Catalysts For Selective Hydrogenation Research Articles

Mesoporous silica gel doped with terbium, cerium and modified with silver as an efficient and selective catalyst for hydrogenation of unsaturated hydrocarbons

Mesoporous silica gel doped with terbium, cerium and modified with silver as an efficient and selective catalyst for hydrogenation of unsaturated hydrocarbons

Carbon Materials with Different Dimensions Supported Pt Catalysts for Selective Hydrogenation of 3,4-Dichloronitrobenzene to 3,4-Dichloroaniline

In this study, carbon materials with different dimensions, including the typical one-dimensional (1D) carbon nanotube (CNT), two-dimensional (2D) graphene (GF), and three-dimensional (3D) activated carbon (AC), were investigated as a support for Pt catalysts for the selective hydrogenation of 3,4-dichloronitrobenzene (3,4-DCNB) to 3,4-dichloroaniline (3,4-DCAN). Notably, the Pt/CNT catalyst with the lowest dimension exhibited the best conversion of 3,4-DCNB under mild reaction conditions, followed by Pt/GF. Comprehensive characterizations, including XRD, TEM, XPS, and in situ CO DRIFTS, reveal that the dimension of carbon supports plays an important role in the particle size and electronic properties of Pt species, consequently affecting the catalytic performances of Pt catalysts. According to the results, electron-deficient Pt particles with small sizes are more favorable for the hydrogenation of 3,4-DCNB to 3,4-DCAN. In addition, dynamic tests and in situ DRIFTS of 3,4-DCNB indicated that the carbonaceous supports will largely influence the adsorption and activation capacity of the Pt catalysts, so that Pt loaded on CNT and GF are superior to that on the AC. We believe this study will provide good guidance for designing efficient carbon-supported metal catalysts for selective hydrogenation.

Laser-engraved defects in TiO2 support: Enhancing reducibility and redox capability of Pt/TiO2 catalyst for reactive and selective hydrogenation

Titanium dioxide (TiO2) has been studied as catalyst or catalyst support in catalysis. Its synthesis or modification approach controls the structural, optical, and electronic properties. Here we applied laser engraving to the anatase TiO2 and studied the consequent changes in its structure and property as well as the properties of TiO2 supported platinum (i.e., Pt/TiO2) catalyst. The laser engraving enlarged the particle size, formed rutile phase and created defects (i.e., oxygen vacancy (Ov) and Ti3+) in anatase TiO2. This induced band gap change and enhanced visible light absorption. The defects created by laser engraving are stable and more reducible than those existed in the pristine TiO2. The defective TiO2 is structurally stable and has great redox properties. The metal-support interaction in the Pt/defective TiO2 catalyst is stronger than that of the pristine Pt/TiO2 catalyst, which enabled higher reactivity and selectivity in hydrogenation of 3-nitrostyrene and furfuryl alcohol. Laser-engraved TiO2 has been rarely studied for thermal catalysis. This work provides basic understanding of material properties and catalysis application of laser-engraved catalyst supports and catalysts in field of thermal catalysis.

Effect of Cu incorporation on Fe-based catalysts for selective CO2 hydrogenation to olefins

The process of converting CO2 into sustainable chemical feedstock and fuels through reaction with renewable hydrogen has been regarded as a promising direction in energy research. The enhancement of CO2 hydrogenation efficiency to produce valuable hydrocarbons (specifically olefins) on Fe catalysts through Cu modification has been extensively researched. However, there is ongoing vigorous debate regarding the impact of these modifications on catalytic properties and the underlying mechanism. When compared to unprompted iron-based catalysts for CO2 hydrogenation, the choice of desired products, such as C2-C4 and C5+, is relatively low. So, promoters are frequently employed to customize and enhance product distribution. This study investigates how adding Cu to Fe-based supported catalysts affects their performance in converting CO2 to hydrocarbons, with a specific emphasis on the interaction between Fe and Cu. To achieve this goal, catalysts were created using co-precipitation methods, varying the distribution of Fe and Cu within them. A set of composite catalysts underwent testing in a fixed bed setup using a reactant gas mixture at 350 °C and 30 bar pressure. Analysis techniques such as XRD, SEM, TEM, NH3-TPD, H2-TPR, and N2 adsorption-desorption isotherms revealed the presence of iron-copper interaction within the composite catalysts. This interaction between the two components synergistically enhances the catalytic activity in CO2 hydrogenation.

Active Sites for CO2 Hydrogenation to Methanol: Mechanistic Insights and Reaction Control.

Catalytic CO2 conversion to methanol is a promising way to extenuate the adverse effects of CO2 emission, global warming and energy shortage. Understanding the fundamental features of CO2 activation and hydrogenation at the molecular level is essential for carbon utilization and sustainable chemical production in the current climate crisis. This review explores the recent advances in understanding the design of catalysts with desired active sites, including single-atom, dual-atom, interface, defects/vacancies and promoters/dopants. We focused on the design of various catalytic systems to enhance their catalytic performances by stabilizing active metal in a catalyst, identifying the unique structure of active species, and engineering coordination environments of active sites. Mechanistic insights provided by advanced operando and in situ spectroscopies were also discussed. Moreover, the review highlights the key factors affecting active sites and reaction mechanisms, such as local environments, oxidation states, and metal-support interactions. By integrating recent advancements and relating knowledge gaps this review aims to endow an inclusive overview of the field and guide future research toward more efficient and selective catalysts for CO2 hydrogenation to methanol.

Preparation of Ni-Cu-C composite catalysts prepared from mixed nickel and copper hydroxides for selective hydrogenation of 4-nitrophenol

A high-performance Ni-Cu-C composite catalyst was prepared from mixed nickel hydroxide and copper hydroxide, which were obtained by coprecipitation, by thermal treatment with acetylene-containing gas at 120 °C followed by hydrogen reduction at 180 °C. The characterization results of XRD, TEM, XPS, and H2-TPR measurements confirmed the presence of nickel carbide (Ni3C), copper carbide (CuxC), Cu, and Ni in the matrix of amorphous carbon in the composite catalyst. The mild preparation temperature and the porous carbon shell layers prevented the nano-sized particles from aggregation. The formation of interstitial Ni3C and CuxC significantly enhanced the dissociation of molecular hydrogen, accelerating the selective hydrogenation of 4-nitrophenol (4-NP) to yield 4-aminophenol (4-AP) at relatively mild conditions (80 °C and 1.0 MPa hydrogen pressure). The catalytic performance of the composite catalysts depended strongly on the Ni/Cu molar ratio, with an optimal Ni/Cu molar ratio of 4. In addition, the composite catalyst showed high conversion and selectivity to the corresponding aniline in the selective hydrogenation of other nitroarenes, including nitrobenzene, 4-nitrotoluene, 4-nitrochlorobenzene, 4-nitrobenzaldehyde, 4-nitroacetophenone, and 2-nitroaniline. The catalyst offers a novel approach to rational design and preparation of high-performance abundant metal catalysts for selective hydrogenation of nitroarenes.

Heteroatoms‐Stabilized Single Palladium Atoms on Amorphous Zeolites: Breaking the Tradeoff between Catalytic Activity and Selectivity for Alkyne Semihydrogenation

AbstractAs a fundamental industrial catalytic process, the semihydrogenation of alkynes presents a challenge in striking a balance between activity and selectivity due to the issue of over‐hydrogenation. Herein, we develop an efficient catalytic system based on single‐atom Pd catalysts supported on boron‐containing amorphous zeolites (Pd/AZ−B), achieving the tradeoff breaking between the activity and selectivity for the selective hydrogenation of alkynes. Advanced characterizations and theoretical density functional theory calculations confirm that the incorporated B atoms in the Pd/AZ−B can not only alter the geometric and electronic properties of Pd atoms by controlling the electron migration from Pd but also mitigate the interaction between alkene and the catalyst supports. This boosts the exceptional catalytic efficacy in the semihydrogenation of phenylacetylene to styrene under mild conditions (298 K, 2 bar H2), achieving a recorded turnover frequency (TOF) value of 24198 h−1 and demonstrating 95 % selectivity to styrene at full conversion of phenylacetylene. By comparison, the heteroatom‐free amorphous zeolite‐anchored Pd nanoparticles and the commercial Lindlar catalyst have styrene selectivities of 73 % and 15 %, respectively, under identical reaction conditions. This work establishes a solid foundation for developing highly active and selective hydrogenation catalysts by controllably optimizing their electronic and steric properties.

Heteroatoms-Stabilized Single Palladium Atoms on Amorphous Zeolites: Breaking the Tradeoff between Catalytic Activity and Selectivity for Alkyne Semihydrogenation.

As a fundamental industrial catalytic process, the semihydrogenation of alkynes presents a challenge in striking a balance between activity and selectivity due to the issue of over-hydrogenation. Herein, we develop an efficient catalytic system based on single-atom Pd catalysts supported on boron-containing amorphous zeolites (Pd/AZ-B), achieving the tradeoff breaking between the activity and selectivity for the selective hydrogenation of alkynes. Advanced characterizations and theoretical density functional theory calculations confirm that the incorporated B atoms in the Pd/AZ-B can not only alter the geometric and electronic properties of Pd atoms by controlling the electron migration from Pd but also mitigate the interaction between alkene and the catalyst supports. This boosts the exceptional catalytic efficacy in the semihydrogenation of phenylacetylene to styrene under mild conditions (298 K, 2 bar H2), achieving a recorded turnover frequency (TOF) value of 24198 h-1 and demonstrating 95 % selectivity to styrene at full conversion of phenylacetylene. By comparison, the heteroatom-free amorphous zeolite-anchored Pd nanoparticles and the commercial Lindlar catalyst have styrene selectivities of 73 % and 15 %, respectively, under identical reaction conditions. This work establishes a solid foundation for developing highly active and selective hydrogenation catalysts by controllably optimizing their electronic and steric properties.

Unveiling the effects of support crystal phase on Cu/Al2O3 catalysts for furfural selective hydrogenation to furfuryl alcohol

Support crystal phase plays a crucial role in the controlled CO hydrogenation over the supported catalysts. Herein, the effects of Al2O3 crystal phase (α, θ, η, and γ) on the supported Cu-based catalyst is highlighted for furfural (FAL) hydrogenation to furfuryl alcohol (FA). The evaluation results show that Cu/η-Al2O3 exhibits the best performance (FAL conversion: 99.7 %, FA selectivity: 94.0 %), highest TOF value (29.3 h−1) and lowest apparent activation energy (66.3 kJ/mol). The comprehensive characterizations unravel that Cu/η-Al2O3 has the smallest Cu nanoparticles and the highest content of Cu+ and Cu0, which facilitates H2 dissociation and FAL adsorption. The reaction mechanisms suggest that Cu/η-Al2O3 has the strongest FAL adsorption and FA desorption capacity. Moreover, it is demonstrated that FAL is linear chemical adsorption on the catalyst surface in the η1(O) configuration, which avoids the furan ring hydrogenation, and thereby, results in the high FA selectivity. This work would provide some references for developing the high-efficiency CO hydrogenation catalysts.

Alloying and Segregation in PdRe/Al2O3 Bimetallic Catalysts for Selective Hydrogenation of Furfural

X-ray absorption fine structure (XAFS) spectroscopy, temperature-programmed reduction (TPR), and temperature-programmed hydride decomposition (TPHD) were employed to elucidate the structures of a series of PdRe/Al2O3 bimetallic catalysts for the selective hydrogenation of furfural. TPR evidenced low-temperature Re reduction in the bimetallic catalysts consistent of the migration of [ReO4]− (perrhenate) species to hydrogen-covered Pd nanoparticles on highly hydroxylated γ-Al2O3. TPHD revealed a strong suppression of β-PdHx formation in the reduced catalysts prepared by (i) co-impregnation and (ii) [HReO4] impregnation of the reduced Pd/Al2O3, indicating the formation of Pd-rich alloy nanoparticles; however, reduced catalysts prepared by (iii) [Pd(NH3)4]2+ impregnation of calcined Re/Al2O3 and subsequent re-calcination did not. Re LIII X-ray absorption edge shifts were used to determine the average Re oxidation states after reduction at 400 °C. XAFS spectroscopy and high-angle annular dark field (HAADF)-scanning transmission electron microscopy (STEM) revealed that a reduced 5 wt.% Re/Al2O3 catalyst contained small Re clusters and nanoparticles comprising Re atoms in low positive oxidation states (~1.5+) and incompletely reduced Re species (primarily Re4+). XAFS spectroscopy of the bimetallic catalysts evidenced Pd-Re bonding consistent with Pd-rich alloy formation. The Pd and Re total first-shell coordination numbers suggest that either Re is segregated to the surface (and Pd to the core) of alloy nanoparticles and/or segregated Pd nanoparticles are larger than Re nanoparticles (or clusters). The Cowley short-range order parameters are strongly positive indicating a high degree of heterogeneity (clustering or segregation of metal atoms) in these bimetallic catalysts. Catalysts prepared using the Pd(NH3)4[ReO4]2 double complex salt (DCS) exhibit greater Pd-Re intermixing but remain heterogeneous on the atomic scale.

Boosting hydrogenation properties of supported Cu-based catalysts by replacing Cu0 active sites

Balancing the Cu+/Cu0 ratio is a common strategy to improve catalytic activity of Cu-based catalysts but is still constrained by low atomic utilization and the inherent nature of charge distribution. Herein, we reported a strategy of replacing the Cu0 active sites in Cu-based catalysts by constructing bimetallic sites on ceria, which consist of spatially separated trace amounts of palladium metal and plate-shaped Cu+ clusters with one-atom layers. The catalytic activity of the prepared Cu100Pd1/CeO2-FA catalyst (using formic acid) was 4 times that of conventional Cu100Pd1/CeO2-H catalyst in selective hydrogenation of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan, even outperforming some existing noble metal catalysts. Multiple characterizations and theoretical calculations demonstrated that the Pd atom is the heterolytic activation site for H2 molecules while plate-shaped Cu+ metal clusters act as effective hydrogenation places. This directional control involving both spatial relationship and electronic structure of the active site provides a new strategy for designing hydrogenated catalysts.

Performance of PdAu/Al2O3 egg-shell catalyst with isolated Pd1 sites for selective hydrogenation of acetylene

A herein proposed PdAu/Al2O3 egg-shell catalyst for selective acetylene hydrogenation combines two factors to provide perfect performance: isolation of Pd1 active sites by Au and an egg-shell distribution of the active phase across the catalyst pellets. The PdAu/Al2O3 catalyst exhibits high acetylene hydrogenation activity at the level of Pd-catalysts and high intrinsic ethylene selectivity of Au-catalysts.

Acetylene Semihydrogenation over Pd-Bi Intermetallic Compounds: A DFT Combined with Microkinetic Modeling Study.

Acetylene semihydrogenation is an important process both theoretically and experimentally. Pure Pd catalysts usually suffer from limited selectivity for ethylene products and poor stability. Pd-Bi bimetallic compounds are synthesized and show not only excellent catalytic performance but also remarkable long-term stability. However, the detailed mechanism is still unclear. In this paper, the acetylene semihydrogenation mechanism on Pd(100), Pd3Bi1(100), and Pd1Bi1(100) is studied by density functional theory (DFT) calculation and microkinetic modeling. Adding Bi causes the surface d-band center (εd) to move to a lower energy, and the adsorption strength of the intermediate becomes weaker. Besides, ethylidyne (CCH3) formation becomes more difficult on the Pd-Bi alloy due to the lack of continuous surface Pd atoms. As a spectator, CCH3 deactivates the Pd and Pd-Bi alloys by a steric effect. However, the selectivity for ethylene on the Pd-Bi alloy is still high because of the weakly bonded ethylene. We found the relationship between εd and the catalysts' activity and selectivity. This study may supply some clues for the design of selective hydrogenation catalysts.

Manufacturing Single-Atom Alloy Catalysts for Selective CO2 Hydrogenation via Refinement of Isolated-Alloy-Islands.

Single-atom alloy (SAA) catalysts exhibit huge potential in heterogeneous catalysis. Manufacturing SAAs requires complex and expensive synthesis methods to precisely control the atomic scale dispersion to form diluted alloys with less active sites and easy sintering of host metal, which is still in the early stages of development. Here, we address these limitations with a straightforward strategy from a brand-new perspective involving the 'islanding effect' for manufacturing SAAs without dilution: homogeneous RuNi alloys were continuously refined to highly dispersed alloy-islands (~ 1 nm) with completely single-atom sites where the relative metal loading was as high as 40%. Characterized by advanced atomic-resolution techniques, single Ru atoms were bonded with Ni as SAAs with extraordinary long-term stability and no sintering of the host metal. The SAAs exhibited 100% CO selectivity, over 55 times reverse water-gas shift (RWGS) rate than the alloys with Ru cluster sites, and over 3-4 times higher than SAAs by the dilution strategy. This study reports a one-step manufacturing strategy for SAA's using the wetness impregnation method with durable high atomic efficiency and holds promise for large-scale industrial applications.

Noble Metal-Coated Cu Nanoparticle Catalysts for Selective Hydrogenation of Nitrobenzene: Modifying Properties of Noble Metal

Noble Metal-Coated Cu Nanoparticle Catalysts for Selective Hydrogenation of Nitrobenzene: Modifying Properties of Noble Metal

Macroporous Poly(hydromethylsiloxane) Networks as Precursors to Hybrid Ceramics (Ceramers) for Deposition of Palladium Catalysts.

Poly(hydromethylsiloxane) (PHMS) was cross-linked with 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D4Vi) in water-in-oil High Internal Phase Emulsions to form macroporous materials known as polyHIPEs. It was shown that in the process of pyrolysis under Ar atmosphere at 520 °C, the obtained polyHIPEs were converted to ceramers with high yields (82.8-88.0 wt.%). Structurally, the obtained ceramers were hybrid ceramics, i.e., they consisted of Si-O framework and preserved organic moieties. Macropores present in the polyHIPE precursors remained in ceramers. Ceramers contained also micro- and mesopores which resulted from the precursor's mass loss during pyrolysis. Total pore volume and BET specific surface area related to the existence of micro- and mesopores in ceramers depended on the PHMS: D4Vi ratio applied in polyHIPE synthesis. The highest total pore volume (0.143 cm3/g) and specific surface area (344 m2/g) were reached after pyrolysis of the precursor prepared with the lowest amount of D4Vi as compared to PHMS. The composite materials obtained after deposition of PdO nanoparticles onto ceramers followed by reduction of PdO by H2 were active and selective catalysts for phenylacetylene hydrogenation to styrene.

Silicalite‐1 encapsulated Cu‐based catalyst for selective hydrogenation of maleic anhydride to γ‐Butyrolactone

γ‐Butyrolactone (GBL) is an important product of the hydrogenation reaction of maleic anhydride (MA). In this study, Cu@Silicalite‐1 (Cu@S1) catalyst with 20% Cu loading was synthesized using a combination of impregnation & solid‐phase synthesis. The effect of Cu and Silicalite‐1 zeolite binding methods on the MA hydrogenation was investigated methodically. MA conversion reached 96.2% and GBL selectivity reached 27.6% at 240 °C, with maintained catalytic activity after propionic acid corrosion for 150 h on the Cu@S1 catalyst. S1 zeolite as a critical factor for significant effect on MA selective hydrogenation raction over Cu‐based catalysts, it was conducive to improving GBL selectivity and reducing the generation of propionic acid (PA) by‐products. The encapsulation of Cu particles by S1 zeolite promoted metal dispersion, increased the hydrogenation activity and promoted the adsorption of reactants, which provided a reference for improving the acid and water resistance of the catalysts

Enhanced selective hydrogenation of CO2 to CH4 on molybdenum carbide hollow sphere catalyst

AbstractHerein, methane (CH4) production in carbon dioxide (CO2) hydrogenation by hydrogen (H2) is enhanced by reducing surface carbon deposits on molybdenum carbide (Mo2C) hollow spheres. When surface carbon deposits present on Mo2C hollow spheres, CO2 conversion is 9.9%, and CO and CH4 are both produced from CO2 hydrogenation, with CO and CH4 selectivity of 58.4% and 41.6%, respectively. When surface carbon deposits absent on Mo2C hollow spheres, CO2 conversion increases to 18.6%, and CO2 hydrogenation to CH4 is enhanced, with a 100% CH4 selectivity. Reducing surface carbon deposits on Mo2C hollow spheres changes the CO2 adsorbed on Mo2C hollow spheres from a monodentate structure to a bidentate structure which prefers to undergo hydrogenation to CH4, thus enhancing CH4 formation from CO2 hydrogenation. These results open a new way to fabricate more efficient noble‐metal‐free catalysts for selective CO2 hydrogenation.

Nickel Nanoparticles on Hydroxyl and Defect-rich Hollow Carbon Spheres as Catalysts for Efficient Selective Hydrogenation of Phenol

Nickel Nanoparticles on Hydroxyl and Defect-rich Hollow Carbon Spheres as Catalysts for Efficient Selective Hydrogenation of Phenol

CO2 hydrogenation to methanol on efficient Pd modified α-MoC1−x catalysts

It is a potentially desirable process of utilizing CO2 as a feedstock to make valuable chemicals such as methanol. Results from the current study demonstrate Pd modified α-MoC1−x is a high active and selective catalyst for CO2 hydrogenation to methanol. α-MoC1−x is active for both methanol synthesis and RWGS reaction. The addition of 0.1 wt% Pd to α-MoC1−x decreases the CO2 hydrogenation reaction activation energy and increases the CH3OH selectivity due to the H2 spillover effect of Pd. RWGS + CO-hydro pathway as a non-competitive parallel pathway to the dominant formate pathway is verified on Pd/α-MoC1−x/C-N, which increases threefold methanol STY compared with α-MoC1−x/C-N catalyst. This work supplies a feasible strategy for creating a dual active site to enhance the efficiency of methanol synthesis.